Molecular sieves mesoporous structures

The continuous effort of numerous academic and industrial laboratories around the world has resulted in recent years in successful synthesis of a number of new porous materials including new structural types of zeolites and zeolypes, siliceous and non-siliceous mesoporous molecular sieves, mesoporous zeolite single crystals, and micro/mesoporous or micro/macroporous composite materials of different chemical compositions. As a consequence of the success of basic research in this area, zeolites have found new industrial applications. 

Since the discovery by researchers at Mobil of a new family of crystalline mesoporous materials (1), a large effort has been expended on synthesis, characterization, and catalytic evalrration (2). MCM-41 is a one-dimerrsiorral, hexagonal structure. MCM-48 is a cubic structine with two, norrintersecting pore systems (3). MCM-50 is a layered stractme with silica sheets between the layers (4). Many scientists also looked into other mesoporous materials, of note the HMS (Hexagonal Molecular Sieve) family (5) and SBA-15 (acronym derived from Santa Barbara University) (6), bnt to date few materials have been both catalytically significant and inexpensive to synthesize. 

The development of composite micro/mesoporous materials opens new perspectives for the improvement of zeolytic catalysts. These materials combine the advantages of both zeolites and mesoporous molecular sieves, in particular, strong acidity, high thermal and hydrothermal stability and improved diffusivity of bulky molecules due to reduction of the intracrystalline diffusion path length, resulting from creation of secondary mesoporous structure. It can be expected that the creation of secondary mesoporous structure in zeolitic crystals, on the one hand, will result in the improvement of the effectiveness factor in hydroisomerization process and, on the other hand, will lead to the decrease of the residence time of products and minimization of secondary reactions, such as cracking. This will result in an increase of both the conversion and the selectivity to isomerization products. 

The higher conversion in the presence of Ti-beta is probably a result of the higher temperature (343 v.v. 323 K). Diffusional constraints cannot account for the observed differences in selectivity. Ti-beta and TS-1 are distinctly more selective than the mesoporous material. Recalling that tetrapodal titanium sites are more predominant in the former two molecular sieves although tripodal titanium sites are the major surface species over the latter mesoporous material (Section II), we infer that the data indicate that high epoxidation selectivity is probably correlated with the presence of tetrapodal structures in these two molecular sieves. This correlation is discussed in Section VI. 

The majority of the titanium ions in titanosilicate molecular sieves in the dehydrated state are present in two types of structures, the framework tetrapodal and tripodal structures. The tetrapodal species dominate in TS-1 and Ti-beta, and the tripodals are more prevalent in Ti-MCM-41 and other mesoporous materials. The coordinatively unsaturated Ti ions in these structures exhibit Lewis acidity and strongly adsorb molecules such as H2O, NH3, H2O2, alkenes, etc. On interaction with H2O2, H2 + O2, or alkyl hydroperoxides, the Ti ions expand their coordination number to 5 or 6 and form side-on Ti-peroxo and superoxo complexes which catalyze the many oxidation reactions of NH3 and organic molecules. 

Since this initial work there has been a plethora of literature on mesoporous molecular sieves. In addition to the silica and aluminosilicate frameworks similar mesoporous structures of metal oxides now include the oxides of Fe, Ti, V, Sb, Zr, Mn, W and others. Templates have been expanded to include nonionic, neutral surfactants and block copolymers. Pore sizes have broadened to the macroscopic size, in excess of 40 nm in diameter. A recent detailed review of the mesoporous molecular sieves is given in ref [73]. Vartuli and Degnan have reported a Mobil M41S mesoporous-based catalyst in commercial use, but to date the application has not been publicly identified.[74]. 

The first part of the book documents the history, structure, chemistry, formulation and characterizations of zeolites in Chapters 1-4. The past 60 years have seen a progression in molecular sieve materials from aluminosilicate zeolites to micro-porous silica polymorphs, microporous aluminophosphate-based polymorphs, metallosihcate and metallophosphate compositions, octahedral-tetrahedral frameworks, mesoporous molecular sieves and, most recently, hybrid metal organic frameworks (MOFs). 

The X-ray powder diffraction patterns of the parent materials showed the hexagonal structure characteristic for MCM-41 and SBA-15, and the cubic structure for MCM-48, respectively. All the patterns matched well with the reported patterns, confirming the successful synthesis of the mesoporous molecular sieves. The intensity of the reflection did not change essentially upon loading the carrier with the organometallic complexes, nor after a catalytic cycle, showing that the mesoporous structures were not affected by incorporation of the catalyst. 

In principle the bicontinuous 3-dimensional network structure of MCM-48 would act as a good catalytic support.[7] However, its lower hydrothermal and thermal stability has led to much less application of MCM-48 in catalysis. Recently, a family of mesoporous molecular sieves (denoted as MSU-G) with vesicle-like hierarchical structure, worm-like mesoporous structure and bicontinuous nano-porous silica had been synthesized.[8-10] It was proposed that highly accessible mesoporous materials could be obtained through different synthetic procedure and composition. 

The structures of mesoporous molecular sieves were closely related to the surfactants to silica ratios.4 Because of the absence of high order reflections on the XRD patterns of all LZC... 

It is known that temperature is a critical factor for the crystallization of zeolites and molecular sieve materials. Since the mesoporous structures can be formed in a wide range of temperature [2], it is essential to investigate a suitable range of temperatures for the formation of integrated MCM-41 structures in fluoride medium. 

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